TW201033239A - Polyurethane resin film material set formed on substrate - Google Patents

Abstract

This invention provides a polyurethane resin film material set formed on a substrate having excellent film strength. The polyurethane resin film material set contains: a polyol obtained by reacting a polycarbonate polyol with a polycaprolactone polyol, and a prepolymer having an isocyanate end obtained by reacting a polytetramethylene glycol with a polyisocyanate. The mass ratio of the polycarbonate polyol to the polycaprolactone polyol is above 65/35. Moreover, the polyol of the polyurethane resin film material set further contains a micropowder like organic metal catalyst for curing at room temperature, and a curing reaction inhibitor.

Description

201033239 IV. Designated representative map: (1) The representative representative of the case is: None. (2) A brief description of the symbol of the representative figure: None. 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: None. 6. Description of the Invention: TECHNICAL FIELD OF THE INVENTION The present invention relates to an unsolvated urethane resin film material formed, for example, on a substrate to be coated. [Prior Art] The use of polyurethane resins involves various fields such as electrical and electronic materials, automotive railway vehicle materials, and civil construction materials. Among the fields of utilization of these polyurethane resins, there are, for example, paints. Polyurethane resin coatings are used in applications such as construction, civil engineering, buildings, and vehicles. The coatings have excellent appearance and good durability. Although polyurethane resin coatings are often used together with organic solvents, this situation has made environmental problems and work safety problems and the like a big problem. In order to solve this problem, various factors have been examined for the water-based and solvent-free resins to be used (for example, refer to Patent Document 1). However, regarding the water system of the former, there is a problem that the work surface lacks the uniformity of the coated surface of 201033239, or the energy and time required for drying, and the water resistance and hydrolysis resistance of the physical surface. In this regard, although the above-mentioned problems caused by the solvation of the latter are accompanied by a small amount of water, the resin solution which is not solvated is not coated because of high viscosity, and conversely, the viscosity of the resin solution is possible for coating. Reduce the problem of insufficient strength or durability of the physical surface. [Previous Technical Literature]

[Patent Document 1] JP-A-2008-303250 SUMMARY OF THE INVENTION [Problems to be Solved by the Invention] The present invention has been made in view of the above problems, and provides an excellent film strength under solvent-free conditions. The polyurethane resin film material group on the substrate is intended. [Technical means for solving the problem] The polyurethane resin film material group formed on the substrate of the present invention is characterized by 'polycarbonate polyol and poly caprolact one polyol (poly caprolact one polyol) The polyol obtained by the reaction, and a prepolymer having an isocyanate group end obtained by reacting polytetramethylene glycol with polyisocyanate, and a polycarbonate polyol to polycaprolactone The ratio of the alcohol is 65/35 or more by mass. The urethane resin film material group formed on the substrate of the present invention is characterized in that it is preferable that the polyol and the prepolymer having the isocyanate group end are liquid at normal temperature. The urethane resin film material group formed on the substrate of the present invention is characterized in that the polyhydric alcohol further comprises an organic metal catalyst for hardening reaction at a normal temperature and a curing reaction inhibitor. In the polyurethane resin film material group formed on the substrate of the present invention, it is preferable that the polyol is composed of a polycarbonate polyol, a polyhexanol, and an aliphatic diol (al iphat). The reaction of ic giyc〇1). The polyurethane resin film material group formed on a substrate of the present invention is characterized in that 'the preferred polycarbonate polyol is 1,6-hexanediol and dialkyl carbonate. (dialkyl carb〇nate) reaction derived. The polyurethane resin film material group formed on the substrate of the present invention is characterized in that it is preferred that the polyisocyanate is an aliphatic diisocyanate. The polyurethane resin film material group formed on the substrate of the present invention is characterized in that 'the preferred aliphatic diisocyanate is hexamethy 1 ene di i socyanate. a polyurethane resin film material group formed on a substrate, a polyol obtained by reacting a polycarbonate polyol with a polycapro lac tone polyol, and a polytetramethylene glycol a prepolymer having an isocyanate group end obtained by reacting with polyisocyanate, and the ratio of the polycarbonate polyol to the polycaprolactone polyol 201033239 is 65/35 by mass or more. Therefore, the polyurethane film formed on the substrate is excellent in strength. [Embodiment] The embodiment of the present invention will be described below. The polyurethane resin film material group (hereinafter simply referred to as a urethane resin film material group) formed on a substrate in the present embodiment is used, for example, as a coating material to form a coating film on a substrate to be coated. However, the present invention is not limited thereto, and may be used for forming a polyurethane resin film on another substrate as long as the effect of the present invention is produced. The polyurethane resin film material group of the first embodiment of the present embodiment described below will have a polyol and have a polyol. The isocyanate-based prepolymers are separately managed and used in combination with a curing catalyst at the time of film formation. Therefore, the polyol and the prepolymer having an isocyanate group end are stored for a long period of time and have excellent storage stability at the time of use. In the urethane resin film material group of the second embodiment of the present embodiment, φ is used in an organic metal catalyst for curing reaction and a curing reaction inhibitor which are finely powdered at a normal temperature in a polyol. Therefore, the polyurethane resin film material group is excellent in the usability at the time of use. The polyurethane resin film material group of the first and second examples of the present embodiment is an unsolvated film material which does not contain an organic solvent which may cause any environmental problems or the like. First, a polyurethane resin film material group formed on a substrate in the first example of the present embodiment will be described. The polyurethane resin film material group of the first example is a polyol obtained by reacting polycarbonate polyol 5 201033239 with a polycaprolactone polyol, and a heteroquinone obtained by reacting polytetramethylene glycol with polyisocyanuric acid. The prepolymer of the acid ester group is formed, and the ratio of the polycarbonate polyol to the polycaprolactone polyol (polycarbonate polyol/polycaprolactone polyol) is 65/35 by mass or more. Either or both of the polyol and the prepolymer having an isocyanate group end may be solid at normal temperature. However, from the viewpoints of availability during storage and transportation, and when the two are blended at the time of formation of the medium, the curing reaction is not required to be heated and melted. The polyol and the prepolymer having the isocyanate end are preferred. It is a liquid at room temperature. The polyacetate is one of the polyhydric alcohol raw materials, and the type thereof is not particularly limited, and may be appropriately reacted, for example, by dehydrochlorination of a short-chain polyol with phosgene (ph〇Sgene) or a short-chain polyol and carbonic acid. A transesterification condensation reaction of a low molecular weight carbonate such as diaikyl carbonate, alkylene carbonate or diary 1 carbonate. The short-bond polyol, such as ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5 -decanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 3-methyl-1,5 - pentanediol, dimethylol heptane, diethylene glycol, dipropylene glycol, neopentyl glycol, diethylene glycol, dipropylene glycol, cyclohexane-1,4-diol, cyclohexene*-1 , 4-diterpene alcohol, dimer acid diol, glycerin, trimethoprim, double-acceptance, A(bi sphenol A), ethylene oxide, and propylene oxide adduct, Those whose molecular weight is less than 500. Dialkyl carbonate such as dinonyl carbonate, carbonic acid diethyl ester, etc., carbonic acid 201033239 thin vinegar such as ethylene carbonate, propylene carbonate, etc., diaryl carbonate such as carbonic acid Diphenyl carbonate. These may be used alone or in combination of two or more.

However, from the viewpoint of further improving the mechanical strength of the obtained urethane resin film, it is preferred to use a polycarbonate polyol which exhibits a linear aliphatic diol which imparts mechanical strength via crystallinity, particularly 16-hexanediol and It is preferred that the diester carbonate reaction is carried out. The polycaprolactone polyol which is one of the polyol raw materials can be one or both of caprolactone and alkyl-substituted ε-caprolactone, using, for example, a short-chain polyol used in the aforementioned polycarbonate as a starter. The ring is combined to obtain. From the viewpoint of easy adjustment of the molecular weight of the polyol or high storage stability, the polyol is preferably obtained by transesterification of a polycarbonate polyol and a polycaprolactone polyol, and then blending with an aliphatic alcohol. Aliphatic diols such as ethylene glycol, 1,2-propanediol, 1,3-propylene glycol, 1,2-butanediol, butanediol, 14-butanediol, u-pentanediol, 3-methyl Decapentanediol, u-hexanediol, u-octanediol, U-decanediol, neopentyl glycol, dimethyl ketone, diethylene glycol, dipropylene glycol, decyl alcohol, and the like. From the viewpoint of further increasing the mechanical strength of the obtained polyurethane resin crucible, the aliphatic diol is preferably a molecular weight of 200 or less, and is preferably an optimum μ. Specifically, the proportion of the polyol raw material is the ratio of the polyacetate polyhydric phenol polyol (polycarbonate polyol/polycaprolactone polyol); the ratio is 65/35 μ. The upper limit of _ is not specifically cut into polycarbonate. 7 201033239 The polyol is close to about 100%, but the point of view taken as a liquid from the current policy is preferably 75% (ratio is 75/25) or less.犮 _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ The diol diol polycaprolactone polyol] The molecular weight of the polytetramethylene glycol which is one of the raw materials of the prepolymer having an isocyanate group terminal is not particularly limited, but the viewpoint of the appearance of the obtained urethane resin film is preferably The average molecular weight is 5 Å or more. The polyisocyanate which is the other raw material of the prepolymer having an isocyanate group terminal is not particularly limited, and is, for example, 2,4-tolyl diisofluoride (hereinafter referred to as 2, 4-TDl), 2,6-TDI, 4,4,-diphenylmethane diisocyanate (hereinafter referred to as 4,4,-MDI), 2,4,-MDI, 2,2,-MDI, 1,5 - 1,5-naphthylene di isocyanate, 1,4-naphthyl diisocyanate, p-phenylene di isocyanate, isophthalonitrile diisocyanate, o-diphenylene Diisocyanate (〇_xylylene diisocyanate), m-diphenylene diisocyanate, p-pair Phenylenic diisocyanate, tetramethyl xylylene diisocyanate, 4,4, diphenyl ether diisocyanate, 2-n-diphenyl-4,4,-diisocyanate, 2,2 '_Diphenylpropane-4,4,-diisocyanate, 3,3,-dimethyldiphenylmethane-4,4'-diisocyanate, 4,4'-diphenylpropane diisocyanate, 3, Aromatic diisocyanate such as 3'-dimethoxydiphenyl-4,4'-diisocyanate, tetramethylene diisocyanate or hexamethylene diisocyanate (below) HDI), 2_201033239 methyl-1,5-pentane diisocyanate, 3-methyl-1,5-pentane diisocyanate, lysinedii socyanate, etc. Aliphatic diisocyanate, isophorone diisocyanate (hereinafter referred to as IPDI), hydrogenated tolylylene diisocyanate, hydrogenated diphenylmethane diisocyanate (hereinafter referred to as HuMDI), hydrogenated xylylene diisocyanate (hereinafter referred to as h6XDI), An alicyclic diisocyanate such as tetramethyldiphenenyl diisocyanate or cyclohexyl diisocyanate, and the foregoing Two or more kinds of mixtures, an adduct modified body of the above organic diisocyanate, a biuret modified body, an ure todic acid modified group, a urethanone An uretonimine modified substance, an isocyanurate modified substance, a carbodiimide modified body, or the like. In the present embodiment, from the viewpoint of easy preparation of the polyurethane film and the appearance and mechanical strength of the obtained polyurethane resin film, it is preferred that the aliphatic diisocyanate is in the form of an aliphatic diisocyanate or an I. Cyanic acid vinegar, especially hexamethylene diisocyanate (rib I) is the best.预 The prepolymer having an isocyanate group terminal has a content of isocyanate of 4 to 12% by mass, and the content of unreacted polyisocyanate is preferably 5% by mass or less. The compounding ratio of the polyol at the time of film formation and the prepolymer having an isofluoride group terminal is not particularly limited, but, preferably, it is 1 mol of a hydroxyl group in a polyol, and a prepolymer having an isocyanate group terminal. The isocyanate group in the medium is 0.90~1.1〇. Next, a polyurethane resin film material group formed on a substrate in the second example of the present embodiment will be described. The polyurethane resin film material group formed on the substrate of the second example is the above-mentioned 9 201033239. The polyol of the polyurethane resin film material group formed on the substrate of the present embodiment further contains a fine powder-like hardening reaction at normal temperature. The organometallic catalyst and the hardening reaction inhibitor. Therefore, in the state in which the organometallic catalyst for the curing reaction is dispersed in the polyol, a so-called usable can be used as compared with the case where a general hardening reaction organometallic catalyst is added to the urethane resin film formed on the substrate. The time is extended to prevent the delay of hardening time. The details are as follows.

The organometallic catalyst is an organometallic compound which acts as a catalyst for generating a hardening reaction in a specific hardening temperature condition, and is not particularly limited, and for example, contains

Sn, Pb, Cd, Zn, Ab Zr, Bi, Mg, Fe, Ti, Cu, Co, Ni,

a maloate compound, an oxide, an ester compound, a mercap1 (ide) compound, and a chelate compound of a metal such as In ' Ca ' γ, Ce, Sr, M〇, u, etc., wherein a normal temperature solid or a mixture. Among the foregoing, it is preferred to use a finely powdered organotin compound at normal temperature.

Organotin compounds, such as dibutyltin distearate, dibutyltin maleate polymer, dibutyltin bis(alkyl maleate), bis(dibutyltin cis-butyl succinate) Butyric acid salt, dibutyl tin s,. - thiochlorocarbonate polymer, dioctyl distearate, dioctyltin succinate polymer, dioxin double (cis succinic acid vinegar) salt, bis (dioctyl cis-butan) Acid alkyl ester) maleate, dioctyl tin s, bismuth thiohydrocarbonate polymer, dioctyl tin di 〇 〇 、, dioctyl tin oxide, etc. Among them, a solid at room temperature can be used. The particle diameter of the organometallic catalyst is preferably 70 AD or less, more preferably 5 0 // m or less. 10 201033239 The amount of the organic metal catalyst to be added to the polyol 'the total amount of the polyol used for the polyurethane resin film material group and the prepolymer having the isocyanate group end is preferably in the range of 50 to 2, OOO ppm, more preferably 80~1, 5〇〇ppm range. The addition of the above organometallic catalyst in order to prepare a desired reactivity does not hinder the addition of the third-order amine catalyst. The hardening reaction inhibitor may contain at least one of citric acid, phosphorous acid, acid lactic acid vinegar, and acid sulfonic acid fia, or a mixture thereof. From the viewpoints of long usable time and short hardening time, Preferably, an acid dish vinegar having a carbon number of 1 to 18 and a mixture of the foregoing may be used. The above acidic dish acid can be, for example, ethyl phosphate, diethyl phosphate, isopryl pyl acid phosphate, butyl acid phosphate, 2-ethylhexyl vinegar ( 2-ethyl hexyl acid phosphate), bis(2-ethylhexyl) acid phosphate, isodecyl acid phosphate, lauryl acid phosphate, Trideyl acid phosphate, stearyl acid phosphate, isostearyl acid phosphate, oleyl acid phosphate, hard acid The amount of the polyhydric alcohol added by the cerium hardening reaction inhibitor such as stearyl acid phosphate is preferably 25 to the total amount of the polyol used in the urethane resin film material group and the prepolymer having the aryl ester group. The range of 1,OOppm, more preferably in the range of 40 to 750 ppm, and even more preferably in the range of 50 to 600 ppm. Next, a method of forming a urethane resin film on a substrate of a urethane resin film material group on a substrate using the first example or the second example forming 11 201033239 of the present embodiment, and using a urethane resin as a coating material on the substrate The method of forming the coating film on the above is taken as an example and is schematically illustrated. First, the polyurethane resin film material group of this embodiment is mixed at room temperature to be equal to the release film, and the film material (raw material) solution is prepared. At this time, the content of the polyhydric alcohol and the prepolymer having an isocyanate group end is adjusted to form, for example, a hydroxyl group of 1 mol in the polyol, and the isocyanate group having an isocyanate group end is 0. 90~1. In the case of the first embodiment of the present embodiment, the curing catalyst is added in an amount of 0.5 part by mass to the mass portion of the mixture of the polyol and the prepolymer having the isocyanate group terminal. When the film material (raw material) is a solid at normal temperature, it is heated to a liquid state at an appropriate temperature. Next, the liquidized film material is applied onto a substrate such as a metal plate, and then dried and cured. In the case of the polyurethane resin film material group of the second example of the present embodiment, the above-mentioned organic metal catalyst and the curing reaction inhibitor are used in combination, but in the present embodiment, i In the case of the urethane resin enamel film material group, the curing catalyst is not particularly limited, and for example, triethylamine, triethyldiamine, N-methylimidazole (imidaz〇le), N-ethylmorpholine can be suitably used. (morpholine), amines such as 1,8-diazabicyclo-5, 4, undecene-7 (dub); containing Sn, Pb, Cd, Zn, A1, &

Malate compounds, oxides, esterified compounds, mercaptide compounds, and chelates of metals such as Mg, Fe, Ti, Cu, Co, Ni, In, Ca, lanthanum, Ce, Sr, Mo, and La Organometallics, etc., specifically, acetic acid #5, octanoic acid kick, monolauryl dibutyltin, dilauryl dioctyl kick (D〇tdl) 12 201033239 and other organic metals. The polyurethane resin film material group or the like formed on the substrate in the present embodiment described above has excellent strength in the polyacetal resin film formed on the substrate. The strength of the urethane resin film was evaluated as TB (tensile strength), EB (extensibility), and TR (breaking strength) as will be described later. The polyurethane resin film material group or the like formed on the substrate of the present embodiment can be suitably used as a coating material or a resin film formed on another substrate. Alternatively, it may be applied to an adhesive, a synthetic leather, a plastic film, or the like. [Examples] The present invention will be further described by way of examples and comparative examples. The invention is not limited to the embodiments described below. (Preparation Example of Polyol) The polyol of one of the materials of the polyurethane resin film material group was prepared by the conditions of Table 1, the nitrogen gas was bubbled in a 2 liter separable flask, and the φ was stirred at 190 ° C. It was obtained by transesterification at 24 hours (60 rpm). [Table 1] 0H-1 OH-2 OH-3 0H-4 OH-5 OH-6 OH-7 OH-8 OH-9 OH-10 1,6-HD 50 70 45 59 56 44 38 PCD-HG- 1000 1000 800 PCD-HG-2000 1000 750 655 891 844 656 562 PCD-HG-5000 630 PCL-210 200 300 50 100 300 400 200 PCL-220 200 PCL-320 100 Hydroxyl price 56 112 112 100 112 112 112 112 112 112 Average functional group number 2 2 2 2.1 2 2 2 2 2 2 Number average molecular weight 2000 1000 1000 1200 1000 1000 1000 1000 1000 1000 Μ Mi: Normal temperature, φ / JDL Normal temperature Normal temperature Normal temperature Normal temperature Normal temperature Normal temperature Normal temperature Normal temperature Normal temperature 1 King liquid Solid Liquid Liquid Liquid Solid Solid Liquid Liquid Liquid 13 201033239 Table 1 and the following tables, the unit amount of the amount of each component to be formulated. The unit of the hydroxyl value is mg KOH/g. Each of the polyol raw materials indicated by the numbers in Table 1 is divided into L: alcohol. (1) is the following. 〇PCD-HG-1_ : 纟16-hexanediol and carbonic acid obtained by the number average molecule 41_. The deacetylated ruthenium PCD-HG-2_...,6-hexanediol and carbonic acid should be obtained by the number average molecular weight of 2_polycarbonate I-de-ethanol anti-para-u-hexanediol and complex acid two...de-ethanol reverse It is desirable to obtain a polycarbonate diol having a number average molecular weight of 5,000. = PCL-21(): the difunctional polycaprolactam with the number average molecular weight of the distillate obtained from the combination of butylene glycol and tetracycline. The initiator is hexamethylene (10) L-22G4 u-butanediol. The di-caprolactone diol having a number average molecular weight of 2000 obtained by ring-opening e_hexyl (tetra) is obtained, and the initiator is ethylene glycol. ~ a fPCL-320: the number of ε-caprolactone ring-opening combined in 4丨 butanediol

Trifunctional polycaprolactone diol having an average molecular weight of 2 Å, and the initiator is trimethylolpropane D (Preparation of polyisocyanate) Polyisocyanate of one of the materials of the urethane resin film material group _ The raw materials of the conditions of Table 2 were prepared by bubbling nitrogen gas in a separable flask and urethaneization reaction for 4 hours. Thereafter, it was obtained by thin film distillation at 14 (Γ, 〇·3Τ〇ΓΓ, removing unreacted HDI. 14 201033239 [Table 2] NCO-1 NCO-2 NCO-3 NCO-4 NCO-5 NCO-6 C-HX HD1 700 660 336 336 712 660 PTG-250 200 PTG-650 300 PTG-1000 340 PTG-2000 2000 PPG-600 288 PPG-1000 340 Yield (% by mass) 45 45 45 45 NC0 (% by mass) 8 5.8 15.7 3.6 9 3.6 21 Viscosity (mPa · s, 25 ° C) 1000 1500 300 Normal temperature solid 300 500 2500 In Table 2, the respective polyisocyanate raw materials are numbered as follows: 〇HDI: hexamethylene diisocyanate OPTG-250: polytetramethylene glycol OPTG-650 having a number average molecular weight of 250: polytetramethylene glycol having a number average molecular weight of 650 OPTG-1 00 0 : polytetramethylene glycol having a number average molecular weight of 1000 〇PTG-200 0 : number average molecular weight Polytetramethylene glycol φ OPPG-600 of 2000: Polypropylene glycol having a number average molecular weight of 600 〇PPG-1 000: Polypropylene glycol having a number average molecular weight of 1000 The C-HX of isocyanate in Table 2 is OC-HX: CORONATE HXCCORONATE ® is a trademark of Nippon Polyurethane Industry Co., Ltd., which is Liuya Isoisocyanurate isocyanurate denatured polyisocyanate, isocyanate content = 21. 0%, viscosity (25 ° C), 2500 mPa·s. (Examples 1 to 12 and Comparative Examples 1 to 6) The alcohol and the polyisocyanate are blended under the conditions of Tables 3 to 5, and the mass of the 15.〇1 mass portion is added as a curing catalyst to 100 parts by mass of the mixed liquid of the multi-column 15 201033239 alcohol and the prepolymer having an isocyanate group end. Diuryl dioctyl tin (DOTDL), modulating polyurethane film (film) and evaluation. For polyols which are solid at room temperature and cured by blending, add a curing catalyst after heat-melting treatment to prepare a polyurethane film. Evaluation was carried out. [Table 3] Example 1 Example 2 Comparative Example 1 Example 3 Comparative Example 2 Comparative Example 3 Polyol 0H-3 OH-3 OH-3 OH-3 OH-3 OH-3 Isocyanate NCO-1 — NCO-2 C-HX NC0-4 NCO-5 NCO-6 Ratio of polyol to isocyanate (isocyanate group (mole ratio) in hydroxyl/isofluorate in polyol) 1/1 1/1 1/ 1 1/1 1/1 1/1 Ratio of polyester to isocyanate (polyol/isocyanate (mass ratio)) 100/106 100/ 145 100/44 100/233 100/93 100/145 Properties of polyol and isocyanate mixture liquid liquid liquid liquid liquid TB 60 40 15 20 5 (unhardened) EB 600 800 250 1000 1000 TR 70 60 15 30 5 [Table 4] Example 4 Example 5 Comparative Example 4 Example 6 Example 7 Comparative Example 5 Example 8 Example 9 Example 10 Example 11 Dimeric Yeast-4 0Η-4 0Η-4 ΟΗ-5 ΟΗ-5 ΟΗ -5 ΟΗ-6 ΟΗ-7 ΟΗ-8 ΟΗ-10 isophthalic acid hydrazine NCO-1 NC0-2 C-HX NCO-1 NCO-2 C-HX NCO-1 NCO-1 NCO-1 NCO-1 Proportion of guanidinium isocyanate (hydroxyl group in polyol / isodecanoic acid s group in isocyanurose (Merce Ή 1/1 1/1 1/1 1/1 1/1 1/1 1/ 1 1/1 1/1 1/1 ratio of polyol 舆 isocyanate (polyol/isocyanate (mass ratio 100/102 100/102 100/43 100/106 100/145 100/44 100/106 100/106 100/ 106 100/106 The property of a mixture of polyisocyanate isocyanate liquid liquid liquid liquid liquid liquid 多元 (multi-fermented often thick «) (multi-fermented room temperature solid «) (polyol normal temperature solid) room temperature liquid 鳗ΤΒ 60 50 10 50 45 10 65 65 50 60 ΕΒ 700 800 150 600 600 30 0 500 550 600 600 TR 70 45 5 80 50 10 75 70 80 70 16 201033239 145] ZT^^ Example 1 (continued in Table 1) Example 12 Comparative Example 6 ^^Polyol 0H-3 0H-8 0H- 9 Cyanate ester NC0-1 NC0-1 NC0-1 "彳卩^^ 疋 成分 成分 成分 i i i i i, b-fflHPCD-HG-2000) / PCL-210 (mass ratio)} 80/20 70/ 30 60/40 Ratio of polyol to isocyanate (polyol/isophthalic acid vinegar (mass ratio)) 100/106 100/106 100/106 Properties of polyol and isocyanate mixture Liquid liquid liquid --- TB 60 50 20 - -- EB 600 600 800 ------ TR ' 70 80 30 (Characteristic evaluation) The liquid immediately after mixing the polyol and the isocyanate of each of the conditions of Example 12 and Comparative Examples 1 to 6 was flowed on the release paper. Upper, with a coating bar (bar

The coater was cast into a film having a thickness of 300 mm x 300 mm. The film was cured at 120 ° C for 10 minutes to obtain a film of the polyurethane film. The following evaluation items were carried out using the polyurethane film as a sample. 〇TB (strength at break) TB was evaluated based on JJS K6251. The unit of TB value is MPa. According to the application, it is desirable to consider the TB value of 20 or more. 〇EB (extension at break) EB was evaluated based on JIS K6251. The unit of the EB value is %. In the case where the EB value is expected to be 300 or more depending on the application, the example and the comparative example are distinguished by the boundary value. 〇TR (Tear Strength) TR was evaluated based on JIS K6252. The unit of the TR value is N/m. According to the application, if the TR value is 30 or more, the value is 17 201033239. The boundary difference is different from the embodiment and the comparative example. (Example 13) i2g of oh-5, 2 g of an organometallic catalyst (NW-96), and a hardening reaction inhibitor of lg (jp-508) were respectively added to a 2 liter separable flask, 25 Stir at °C for 30 minutes. According to this, JP-508 was uniformly mixed with a polyol to obtain a polyol premix (hereinafter referred to as OH-10) in which NW-96 was dispersed in a polyol. NW-96 is an organic tin compound-based catalyst KS-1010A-1 (malic acid di-n-octane. polymer; manufactured by Co-Pharma Co., Ltd.) and an adipate plasticizer ΡΝ-250 (Co., Ltd. ADEKA manufactured by Seiko Chemical Industry Co., Ltd., which is a dispersion-treated product obtained by mixing the three-axis roller into a KS-101 Ο-A with a particle size of up to 3 〇 ν η. Acidic phosphoric acid: a mixture of mono (androso-2-ethylhexyl) and bis(androsine-2-ethylhexanoic acid). The respective temperature is adjusted to 25. (: NC0-1 and OH-10, at 25 (mixed in an atmosphere of 30 seconds). The state immediately after mixing is a state in which the organometallic component is dispersed. 400 g of this mixture is placed in a glass sample having a capacity of 500 cc. In the bottle ❹ “When it is allowed to stand in an atmosphere of 25 ° C, the fluidity is maintained after 5 hours of mixing. The liquid from the mixed 5 hours flows on the release paper and is cast to a thickness of 1 涂布 by the coating bar. The film of the private m, the area of 3 〇〇mm x 3 〇〇 mm was hardened by 15 〇艽 for 3 minutes to obtain a polyurethane film. The obtained polyurethane film had a TB of 50 MPa, an EB of 600%, and a TR of 80 kN/m.

On the other hand, the freshly mixed liquid was poured on a release paper, and a film of a thickness of 10 μm and an area of 3 mm×3 〇〇 min was hardened by a coating bar to cure at 150 ° C for 3 minutes to obtain a polyurethane film. The obtained polyurethane film had a TB of 50 MPa, an EB 18 201033239 of 600%, and a TR of 80 kN/m. (Example 14) 1 g of OH-5, 0.2 g of DOTDL (dilauryl dioctyl tin; normal temperature solid), and O.lg of JP-508 were respectively added to a 2 liter separable flask. The mixture was stirred at 25 ° C for 30 minutes to obtain a polyol premix (hereinafter referred to as 0H-11) in which D0TDL and JP-5 08 were uniformly formed with a polyol. NC0-1 and 0H-11, each adjusted to a temperature of 25 ° C, were mixed under an atmosphere of 25 ° C for 30 seconds. The state immediately after mixing is uniform. 400 g of this mixed solution was placed in a glass sample bottle having a capacity of 500 cc, and when it was allowed to stand in an atmosphere of 25 ° C, no fluidity occurred from the mixing for 30 minutes, and even if the glass bottle was inverted, the liquid did not flow out.

On the other hand, the freshly mixed liquid was poured on a release paper, and a film of a thickness l〇〇#m and an area of 300 mm x 300 mm was cast by a coating bar, and hardened at 15 〇〇c for 3 minutes to obtain a polyurethane film. The obtained polyurethane film had a TB of 50 MPa, an EB of 600%, and a TR of 80 kN/m. [Simple description of the diagram] None. [Main component symbol description] None. 19

Claims (1)

201033239 VII. Patent Application Range: 1. A polyurethane resin film material group formed on a substrate, characterized by 'p-polycarbon bona te polyol and polycaprolactone polyol (polycaprolactone polyol) The polyhydric alcohol obtained by the reaction, and the prepolymer having the isodecanoate end group obtained by reacting polytetramethylene glycol with copolyisocyanate and the polyisocyanate The ratio of the caprolactone polyol is 65/35 or more by mass. 2. The polyaminoxylene resin film material group formed on the substrate according to the first aspect of the invention, wherein the polyol and the prepolymer having an isocyanate group end are in a liquid state at normal temperature. 3. The polyamine eucalyptus membrane material group formed on a substrate according to claim 2, wherein the polyol further comprises an organic metal catalyst for hardening reaction at a normal temperature in a fine powder form. And hardening reaction inhibitors. The polyurethane resin film material group formed on the substrate 10 according to any one of the items of the invention, wherein the polyol is a polycarbonate polyol or a polycaprolactone polyol. And the reaction of aliphatic diol (aliphatic glycol). 5. The polyurethane resin film material group formed on a substrate according to claim 4, wherein the polycarbonate polyol comprises 16-hexane (1,6-heXanediol) and dialkyl carbonate. Derived from diaikyi carbonate. 6. The polyurethane resin film material group formed on the substrate 20 201033239 according to any one of the claims of the third aspect of the invention, which is characterized in that it is an aliphatic diisocyanate. The polyisocyanate 7. The group of the 6th ester resin film material according to the patent application, characterized in that the polyamino-isocyanate formed on the substrate is hexamethylene diisocyanate (hexamethylene). Dii_ya she). 21 201033239 IV. Designated representative map: (1) The representative representative of the case is: None. (2) A brief description of the symbol of the representative figure: None. 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: None. 6. Description of the Invention: TECHNICAL FIELD OF THE INVENTION The present invention relates to an unsolvated urethane resin film material formed, for example, on a substrate to be coated. [Prior Art] The use of polyurethane resins involves various fields such as electrical and electronic materials, automotive railway vehicle materials, and civil construction materials. Among the fields of utilization of these polyurethane resins, there are, for example, paints. Polyurethane resin coatings are used in applications such as construction, civil engineering, buildings, and vehicles. The coatings have excellent appearance and good durability. Although polyurethane resin coatings are often used together with organic solvents, this situation has made environmental problems and work safety problems and the like a big problem. In order to solve this problem, various factors have been examined for the water-based and solvent-free resins to be used (for example, refer to Patent Document 1). However, regarding the water system of the former, there is a coating surface where the working surface is lacking.